Development and calibration of epiphytic lichens as saltfall biomonitors--dry-deposition modelling

Blubber collected from beluga whales and ringed seals during subsistence hunts in the southern Baffin Island region of the Canadian Arctic were analysed for polychlorinated naphthalenes and eight planar PCB congeners (mono-ortho PCBs: 105, 114, 118 and 156; non-ortho PCBs: 77, 81, 126, 169). SigmaPCN (3-7 Cl) concentrations in blubber ranged from 35.9-383 pg/g (lipid weight; lw) in beluga and 35.4-71.3 pg/g (lw) in ringed seal. These represent the first measurements of PCNs in marine mammals in the Canadian Arctic, mammals which are an important part of the traditional diet of the indigenous population. SigmaCoplPCB concentrations were much higher, ranging from 15.5-317 ng/g (lw) in beluga whale blubber and 16.5-40.9 ng/g (lw) in ringed seal blubber. PCNs and coplanar PCBs both exhibit dioxin-like toxicity. Although average sigmaPCN concentrations were less than 1% of sigmaCoplPCBs, PCNs contribute up to 11% of TEQ relative to the coplanar PCBs based on TEFs determined by H4IIE enzyme assays.     

Organochlorine burdens in blood of ringed and bearded seals from north-western Svalbard.

Ringed seal (Phoca hispida) and bearded seal (Erignathus barbatus) are the main prey of polar bears (Ursus maritimus), and information on organochlorines (OCs) in these pinniped species is important to understand the transport, fate and effects of persistent organic pollutants in the Arctic ecosystem. Thus, OCs were analysed in blood samples of bearded and ringed seals from the coastal ecosystem of the north-western Svalbard archipelago (Kongsfjorden, 78.55degrees N). The relative contribution of OCs could be ranked as follows: Ringed seal females: sigmaPCB > sigma DDT > sigma CHL > sigma HCH > HCB > Mirex. Ringed seal males: sigma PCB > or = sigma DDT > sigma CHL > sigma HCH > or = HCB > Mirex. Bearded seal females: sigma PCB > sigma HCH > or = sigma CHL > sigma DDT > Mirex > HCB. Bearded seal males: sigma PCB > sigma DDT > or = sigma CHL > sigma HCH > Mirex > or = HCB. The concentrations of sigmaPCB and sigma DDT were higher in ringed seals than in bearded seals, whereas sigma HCH was higher in bearded than in ringed seals. In ringed seal females and males sigma PCB was 337 +/- 95 ng/g (n= 6) and 625 +/- 443 ng/g (n=6), whereas sigma DDT was 165 +/- 47 ng/g (n=6) and 621 +/- 559 ng/g (n = 6), respectively. In bearded seal females and males, sigmaPCB was 159 +/- 132 ng/g (n = 6) and 248 +/- 93 ng/g (n = 5), whereas sigmaDDT was 46 +/- 41 ng/g (n = 6) and 161 +/- 71 ng/g (n = 5), respectively. The inter-species differences are caused by a higher trophic position of ringed seals in the Svalbard ecosystem compared to bearded seals. OC levels in ringed seals at Svalbard are similar to those reported from the North-American Arctic and in the lower range compared to previously reported data from Svalbard.     

PCBs and organochlorine pesticides in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), 1994-1998

For the first time, organochlorine (OC) contaminants were measured in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), to compare contaminant levels to those previously measured in dead stranded belugas. PCBs, DDTs, toxaphene and chlordane-related compounds were the major OC contaminants detected in 44 belugas biopsied in 1994-1998. SigmaPCB (the sum of 104 congeners) ranged from 2080 to 128,000 ng/g lipid in males (n=34; minimum estimated ages 8-22 years), and from 148 to 44,100 ng/g lipid in females (n=10; minimum estimated ages 7-22 years). The concentrations of PCBs and OC pesticides in the blubber of these whales overlapped those observed in stranded belugas from an earlier study, and demonstrated comparable age and sex-related trends. However, lower proportions of mirex, HCB, DDTs, and many of the highly chlorinated PCBs occurred in the biopsy samples compared to results for blubber from stranded carcasses. Most major OC compounds were present at lower concentrations in the biopsies, but this does not appear to be solely related to age differences between the two groups, or to emaciation in the stranded whales. Nor does it appear to be associated with the use of superficial biopsies, and the possible stratification of lipids and OCs in the blubber layer. Nevertheless, given these possible confounding factors, and the uncertainty in age estimates for the biopsied whales, the results point to the need for careful interpretation of biopsy results when comparing with data taken from the full depth of the blubber mantle in stranded whales. Taken together, results from both biopsied whales and previously studied stranded belugas indicate that PCB and OC pesticide contamination of St. Lawrence beluga whales may occur across a broader range of levels than previously thought, at least for males which formed the largest group in this study, possibly due to different degrees of dietary exposure. It also appears that measuring contaminant concentrations only in stranded whales, may overestimate OC levels in the population as a whole, especially for highly chlorinated OCs.     

Levels and patterns of persistent organochlorines in minke whale (Balaenoptera acutorostrata) stocks from the North Atlantic and European Arctic

Regional variation in PCBs and organochlorine (OC) pesticide concentrations was examined using the blubber of 155 minke whales (Balaenoptera acutorostrata) sampled in seven regions in the North Atlantic and European Arctic, including western and southeastern Greenland, the Norwegian Sea, the North Sea and the Barents Sea. The levels and relative proportions of OCs were also used to examine the boundaries for North Atlantic minke whale stocks previously defined by the International Whaling Commission (IWC). Concentrations of major OC groups (sigmaPCB, 89.1-22 800 ng/g lipid; sigmaDDT, 65.3-6280 ng/g lipid; sigmaCHL, 33.3-2110 ng/g lipid) generally increased from west to east, while HCH concentrations (sigmaHCH, < 1-497 ng/g lipid) showed the opposite trend. Statistical comparison between six regions using sex-adjusted least squared mean concentrations showed that minke whales from the Barents Sea had significantly higher concentrations of EPCBs than those from the Vestfjorden/Lofoten, the North Sea, and west Svalbard, as well as significantly higher sigmaDDT concentrations compared to west Greenland animals. The differences in concentrations suggest that west and southeast Greenland minkes may represent one group of whales, which are distinct from both the Jan Mayen minkes and those from other IWC defined stocks in northern European waters. Principal components analysis using proportions of 71 PCB congeners and 20 OC pesticides (of total OCs) did not reveal any major differences among groups although minkes from the North Sea were distinguished from those from Greenland waters by higher loadings of more highly chlorinated PCBs and recalcitrant OC pesticides. The general similarity in mean levels of sigmaPCBs, sigmaDDT and sigmaCHL, as well as mean principal components analysis scores, among minkes sampled at Jan Mayen, Svalbard, Vestfjorden/Lofoten, the North Sea and the Barents Sea suggests that the whales are quite mobile and may feed in multiple areas within the northeastern Atlantic.     

Determination of toxaphenes in fish and marine mammals

An analytical method for the determination of toxaphene in biological materials using gas chromatography with an electron capture detector (GC-ECD) has been established and validated for three single congeners (chlorinated bornanes (CHB) 26, 50 and 62). The analytical method was based on a method for determination of PCB, DDT and other chlorinated pesticides. To include toxaphene congeners an extra step, adsorption chromatography on silica columns, was introduced to separate the pesticides from PCB. The recovery of CHB-26, 50 and 62 were 97+/-11%, 94+/-10% and 99+/-12%, respectively. Samples from cod, ringed seal and polar bear from the Norwegian arctic environment have been analysed. The levels of CHB-26 and 50 found were 13-55 ng/g fat in cod, 1.3-7.7 ng/g fat in ringed seal and 0.4-119 ng/g fat in polar bear. The levels of CHB-62 were 2.0-13, 0.8-3.4, 0.2-11 ng/g fat in cod, ringed seal and polar bear, respectively.     

Organochlorine contaminant and stable isotope profiles in Arctic fox (Alopex lagopus) from the Alaskan and Canadian Arctic

Arctic fox (Alopex lagopus) is a circumpolar species distributed across northern Canada and Alaska. Arctic fox muscle and liver were collected at Barrow, AK, USA (n=18), Holman, NT, Canada (n=20), and Arviat, NU, Canada (n=20) to elucidate the feeding ecology of this species and relate these findings to body residue patterns of organochlorine contaminants (OCs). Stable carbon (delta 13C) and nitrogen (delta 15N) isotope analyses of Arctic fox muscle indicated that trophic position (estimated by delta 15N) is positively correlated with increasing delta 13C values, suggesting that Arctic fox with a predominantly marine-based foraging strategy occupy a higher trophic level than individuals mostly feeding from a terrestrial-based carbon source. At all sites, the rank order for OC groups in muscle was polychlorinated biphenyls (Sigma PCB) > chlordane-related compounds (Sigma CHLOR) > hexachlorocyclohexane (Sigma HCH) > total toxaphene (TOX) > or = chlorobenzenes (Sigma ClBz) > DDT-related isomers (Sigma DDT). In liver, Sigma CHLOR was the most abundant OC group, followed by Sigma PCB > TOX > Sigma HCH > Sigma ClBz > Sigma DDT. The most abundant OC analytes detected from Arctic fox muscle and liver were oxychlordane, PCB-153, and PCB-180. The comparison of delta 15N with OC concentrations indicated that relative trophic position might not accurately predict OC bioaccumulation in Arctic fox. The bioaccumulation pattern of OCs in the Arctic fox is similar to the polar bear. While Sigma PCB concentrations were highly variable, concentrations in the Arctic fox were generally below those associated with the toxicological endpoints for adverse effects on mammalian reproduction. Further research is required to properly elucidate the potential health impacts to this species from exposure to OCs.     

Can seal eating explain elevated levels of PCBs and organochlorine pesticides in walrus blubber from eastern Hudson Bay (Canada)?

Walrus (Odobenus rosmarus) blubber samples from Inukjuak and Akulivik (East Hudson Bay), Foxe Basin (Igloolik and Hall Beach) and Loks Land (East Baffin Island) were analysed for PCB congeners (ortho and non-ortho substituted) and other persistent organochlorines (DDT, toxaphene, chlordanes, dieldrin, mirex), as well as chlorinated dioxins/furans, to document spatial trends in contaminants in Canadian Arctic marine biota. Samples from 19 of 53 individuals had concentrations of SigmaPCBs greater than 1000 ng g(-1) (wet wt); the remaining individuals had much lower concentrations (50-600 ng g(-1)). Highest concentrations were found in samples from Inukjuak where average concentrations in blubber of females (N = 9) were 1450 +/- 954 ng g(-1) toxaphene, 2750 +/- 1780 ng g(-1) SigmaCHLOR, 2160 +/- 925 ng g(-1) SigmaDDT and 4790 +/- 2380 ng g(-1) SigmaPCB. SigmaPCB and SigmaDDT concentrations greater than 1000 ng g(-1) were unexpected based on previous studies of walrus from Greenland and Alaska. Local contamination was ruled out because levels of all organochlorines were elevated in each animal from Inukjuak, and elevated levels were also found in animals from Akulivik and Loks Land. Walrus from Inukjuak had sigma13C and sigma15N values in muscle intermediate between those of ringed seals (Phoca hispida) and those of walrus from Akulivik with low organochlorine levels. There was a weak but significant correlation between and sigma15N and (log)SigmaPCB. The Inukjuak walrus also had higher proportions of highly chlorinated PCB congeners, and higher DDE/SigmaDDT ratios than walrus from Igloolik or Akulivik. The results suggest that the walrus with elevated organochlorines are feeding at a higher trophic level than those with low levels and are probably utilizing ringed seals for a portion of their diet.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

Organochlorine pesticide residue and PCBs in harbour porpoise (Phocoena phocoena) incidentally caught in Scandinavian waters

During Norwegian and Danish harbour porpoise projects 1987-1991, subcutaneous blubber samples of 34 male harbour porpoises (Phocoena phocoena) were collected. Animals from three geographical locations, ranging from 56 degrees N, 12 degrees E to 71 degrees N, 26 degrees E, were chosen in order to study the organochlorine (OC) contamination in this species inhabiting the northeastern part of the North Atlantic Ocean, the northern North Sea and Kattegat, at the locations of Tufjord, Vestlandet and Gilleleje, respectively. Analytical standards used consisted of the industrial chemicals PCBs (22 individual PCB congeners and 6 industrial mixtures which contained 104 PCB congeners or group of congeners) and HCB, and the organochlorine pesticides DDT, HCH, the cyclodienes endrin, dieldrin and the chlordane metabolites oxychlordane and trans-nonachlor, and heptachlor epoxide. A total of 16 PCB congeners or groups of congeners, all the DDT metabolites except o,p'-DDD, and all the pesticides were detected in all animals. The concentrations of sigmaPCB (sum of concentrations of 47 detected PCB congeners) and sigmaDDT (sum of concentrations of all DDT detected compounds) ranged from 3.7-65.3 and 3.2-45.0 microg g(-1) lipid weight, respectively. The range of mean concentrations of dieldrin, endrin and trans-nonachlor was 1-3 microg g(-1), while mean concentrations of HCHs, heptachlor epoxide, and HCB were <1 microg g(-1). No significant variation in PCB congener pattern was apparent between geographical areas. The major PCB congeners nos 147/123, 153, 138/163/164, 182/187 and 180 at Gilleleje, Vestlandet and Tufjord represented 53%, 45% and 44% of sigmaPCB, respectively. A significant difference was found between the number of PCB congeners in blubber of newborn and older porpoises. This might indicate the presence of a blood/placenta barrier and/or selective mammary transport of PCBs with specific structures. A significant OC accumulation with age was apparent, with the exception of HCB and HCHs. Geographical differences in the levels of OCs were apparent for all compounds except for dieldrin and heptachlor epoxide. Significantly higher levels of chlordane metabolites (trans-nonachlor and oxychlordane) and endrin were found in the group of animals from the northern location Tufjord, while sigmaDDT, p,p'-DDTs, HCHs and PCBs were highest in the group of animals from the southern location Gilleleje. Highest levels of the o,p'-substituted DDTs were found in specimens from the middle location Vestlandet. These findings indicate little or no regular migration of harbour porpoise between these three locations. No correlations were found between OC concentrations and blubber thickness. Although mean values of sigmaDDT and sigmaPCB were in the lower end of previously reported levels in harbour porpoise from adjacent waters in the eastern part of the North Atlantic Ocean and along the coasts of North America, these levels are relatively high. The organochlorine concentrations in harbour porpoises in the present study were 2-3 times higher than corresponding OC levels detected in harbour seals (Phoca vitulina) from the same areas.     

Organochlorine contaminants in Caspian and harbour seal blubber

Organochlorine contaminants (pesticides and individual polychlorinated biphenyl congeners, PCBs) were measured in Caspian (Phoca caspica) seal blubber and compared with concentrations in Harbour (Phoca vitulina) seal blubber. Concentrations of total dichlorodiphenyltrichloroethane (DDT) and its metabolites were significantly higher in Caspian seal than Harbour seal samples, whereas PCB congeners were significantly higher in Harbour than Caspian seals. Our finding suggests that Caspian seals are exposed to high levels of DDT pesticides. In contrast, PCBs are circulating in this population at much lower levels than in marine mammals from the North Sea.     

Organochlorine contaminants in narwhal (Monodon monoceros) from the Canadian Arctic

Organochlorine pesticides (DDT, chlordane, polychlorinated camphenes (PCCs), dieldrin, hexachloroheclohexanes (SigmaHCH), mirex), polychlorinated biphenyl congeners (PCBs) and chlorobenzenes (SigmaCBz) were determined in blubber and liver of narwhal (Monodon monoceros) collected during 1982-1983 from Pond Inlet on northern Baffin Island in the Canadian Arctic. PCCs were the predominate organochlorines in narwhal blubber, ranging in concentration from 2990 to 13 200 ng g(-1) (wet wt) in males and from 1910 to 8390 ng g(-1) in females. PCCs consisted of two major components, an octachlorobornane and a nonachlorobornane with gas chromatographic retention times of 1.05 and 1.22, relative to 4,4'-DDE. SigmaPCB concentrations in blubber ranged from 2250 to 7290 ng g(-1) in males and from 894 to 5710 ng g(-1) in females. Seven PCB congeners (tetra-, penta- and hexachlorobiphenyls) accounted for 45% of total PCB (SigmaPCB) in narwhal blubber. Narwhal had 1.4- to 8.6-fold higher ratios of tetra- and pentachlorobiphenyls to PCB-153 (2,2',4,4',5,5'-hexachlorobiphenyl), lower 4,4'-DDE/SigmaDDT ratios and lower proportions of trans-nonachlor to total chlordane components than reported for odontocetes living in more contaminated environments. Mean SigmaPCB concentrations in narwhal were 6- to 15-fold lower than in dolphins from the Canadian east coast and belugas from the St Lawrence River estuary, respectively, while PCC levels were from 4- to about 2-fold lower, and SigmaHCH, dieldrin and SigmaCBz differed by <2-fold. The pattern of organochlorines in narwhal tissues suggests they are exposed to proportionally more volatile compounds, and may have less capacity to metabolize some of these compounds, relative to odontocetes living nearer sources of these contaminants.     

Organochlorines in polar bears (Ursus maritimus) at Svalbard

A comprehensive survey on organochlorine (OC) contaminants in polar bears at Svalbard has been undertaken. Subcutaneous tissue, blood and milk have been sampled from anesthetized free-ranging bears of both sexes and different ages in the period from 1990 to 1994. A number of sexually mature females have been fitted with satellite transmitters which make it possible to follow their reproductive behaviour pattern. We report on contamination levels and pattern of PCB congeners, chlordanes, DDT-compounds, HCB and HCH-isomers in the various tissues. The relation of age, sex and reproductive status to OC contamination has been described, and the capacity of polar bears in metabolising OCs has been discussed from the isomer/metabolite composition of residues. Finally, the possible association between OC contamination and reproduction success has been assessed. The PCB levels present in polar bears at Svalbard are extremely high. Especially high levels of higher chlorinated PCBs are found, and they accumulate with age, particularly in males. With females, considerable amounts of OCs are transferred to the offspring via milk. However, more efficient OC transfer between subcutaneous depot lipid and circulatory lipids than from the circulatory system to milk is found particularly for the most lipophilic compounds. The OC pattern in suckling yearlings reflects the low transfer of the highest chlorinated PCBs into maternal milk. The levels of most other OCs, however, are higher in depot lipid of yearlings than in that of their mothers. The polar bears have high capacity to metabolise several OCs. This may protect them against toxic action of the contaminants. No relation between OC levels in females and their ability to get pregnant is found in this preliminary investigation on OC effects on the polar bears at Svalbard.     

Process-diagnostic patterns of chlorobiphenyl congeners in two radiochronologically characterized sediment cores from the northern Baffin Bay.

Polychlorinated biphenyl (PCB) patterns were interpreted in two radioisotopically constrained sediment cores from the Arctic ocean in order to seek clues about their large-scale environmental fates. Low but clearly measurable fluxes of individual PCB congeners were observed in deeper layer sediments, corresponding to the past 170 years, in a single dated core from the Baffin Bay shelf. Fluxes of the dominant individual congeners in the surface sediments were 20-100 pg m(-2) d(-1). Combining these data with the sediment data from the Arctic Monitoring and Assessment Program, it appears that the PCB distribution in Arctic surface sediments is governed by the organic carbon (OC) content of the sediments. The historical development of the PCB congener fingerprint suggests that the modern sediments are enriched in medium-chlorinated congeners, implying that there are at least two significant, but distinctly different, sink processes acting on the PCB pool. The relative abundance of light-to-heavy congeners, in mid-shelf marine sediments of similar ages, between 40 degrees N and 76 degrees N latitude suggests a northward dilution of PCBs which is stronger attenuated for heavier congeners, consistent with a temperature-driven global fractionation process. The significant presence of PCB in historical archives pre-dating the organochlorine society, as observed in this and several previous studies, awaits a fuller explanation.     

Profile of persistent chlorinated contaminants,including selected chiral compounds,in wolverine (Gulo gulo) livers from the Canadian Arctic

Wolverines (Gulo gulo) are circumpolar omnivores that live throughout the alpine and arctic tundra ecosystem. Wolverine livers were collected at Kugluktuk (Coppermine), NU (n=12) in the western Canadian Arctic to report, for the first time, the residue patterns of persistent organochlorine contaminants (OCs) in this species. The enantiomer fractions (EFs) of several chiral OCs, including PCB atropisomers, in wolverines were also determined. Results were compared to OC concentrations and EFs of chiral contaminants in arctic fox (Alopex lagopus) from Ulukhaqtuuq (Holman), NT (n=20); a closely related species that scavenges the marine and terrestrial arctic environment. The rank order of hepatic concentrations for sum ( summation operator ) OC groups in wolverines were polychlorinated biphenyls ( summation operator PCB)>chlordane-related components ( summation operator CHLOR)>DDT-related compounds ( summation operator DDT)>hexachlorocyclohexane isomers ( summation operator HCHs). The most abundant OC analytes detected in wolverine liver were PCB-153, PCB-180, and oxychlordane (OXY). Wolverine age and gender did not influence OC concentrations, which were comparable to lipid-normalized values in arctic fox. The EFs of several chiral OCs (alpha-HCH, cis- and trans-chlordane, OXY, heptachlor exo-epoxide) and PCB atropisomers (PCB-136, 149) were nonracemic in arctic fox and wolverine liver and similar to those previously calculated in arctic fox and polar bears from Iceland and the Canadian Arctic. Results suggest that these species have similar ability to biotransform OCs. As well, contaminant profiles suggest that terrestrial mammals do not represent the major source of OC exposure to wolverines and that wolverines are scavenging more contaminated prey items, such as marine mammals. While summation operator PCB did not exceed the concentrations associated with mammalian reproductive impairment, future research is required to properly evaluate the potential affect of other OCs on the overall health of wolverines.     

Organochlorine contaminants in seven species of Arctic seabirds from northern Baffin Bay

Organochlorine contaminants (OCs) were determined in liver and fat of seven species of seabirds (Alle alle, Uria lomvia, Cepphus grylle, Rissa tridactyla, Pagophila eburnea, Larus hyperboreus, and Fulmaris glacialis) collected in May/June 1998 from the Northwater Polynya in northern Baffin Bay. OC concentrations ranged over an order of magnitude between seabird species and OC groups, with PCBs having the highest concentrations followed by DDT, chlordane, HCH and ClBz. Positive relationships between delta15N (estimator of trophic level) and OC concentrations (lipid basis) were found for all OC groups, showing that trophic position and biomagnification significantly influence OC concentrations in Arctic seabirds. Concentrations of a number of OCs in particular species (e.g., HCH in P. eburnean) were lower than expected based on delta15N and was attributed to biotransformation. P. eburnea and F. glacialis, which scavenge, and R. tridactyla, which migrate from the south, were consistently above the delta15N-OC regression providing evidence that these variables can elevate OC concentrations. Stable isotope measurements in muscle may not be suitable for identifying past scavenging events by seabirds. OC relative proportions were related to trophic position and phylogeny, showing that OC biotransformation varies between seabird groups. Trophic level, migration, scavenging and biotransformation all play important roles in the OCs found in Arctic seabirds.     

Persistent organochlorine residues in northern fur seal from the Pacific coast of Japan since 1971

The present study was conducted to determine the residue levels of persistent organochlorines such as PCB homologues, DDT and its metabolites, and HCH isomers in the ventral blubber of female northern fur seal (Callorhinus ursinus) collected off Sanriku, the Pacific coast of northern Japan, since 1971. Among the organochlorines examined, the concentrations of PCBs and DDTs were found to be high in all samples. The residue levels of these two contaminants showed a drastic reduction following maturity and then a slight increase after the retirement from pregnancy/menopause. Temporal variation of PCB and DDT residues showed maximum levels around 1976 and then decreased, whereas HCH residue levels revealed a very slow declining pattern. Considering the concentrations and compositions of the residues, the northern fur seal is likely to be exposed to organochlorine contamination deriving from global terms. In this context, continuous contamination has been foreseen with regard to PCB and HCH residues. The pattern of organochlorine residues indicated that the northern fur seal has higher metabolic capacity than Dall's porpoise, while it is comparable to those of larga seal and Steller sea lion.     

Discrimination and thermal degradation of toxaphene compounds in capillary gas chromatography when using split/splitless and on-column injection

Technical toxaphene and a 22-component Reference Mixture were analyzed using capillary gas chromatography with split/splitless injection (SSL) and on-column injection (OC). In both techniques, electron-capture, negative ionization mass spectrometry (ECNI-MS) was used for detection of chlorobornanes, chlorocamphenes and related compounds. Significant discrimination of highly chlorinated congeners was observed as a result of incomplete transfer of these compounds from the vaporizer to the analytical column when using SSL. This resulted in a much lower response for nona- and decachloro congeners than when using OC. In addition, several toxaphene components, especially the chlorobornanes with gem dichloro substitution on the six-member carbon ring, undergo thermal degradation when using SSL. Some of these congeners are major components of technical toxaphene, but generally are not present, except at low concentrations, in environmental and biological samples. Therefore, technical toxaphene may be discriminated and/or degraded differently than toxaphene compounds in environmental samples when using SSL. This results in significant bias of the quantitative data when using the technical material as a reference. OC suffers much less from these deficiencies and, therefore, is a preferable technique for toxaphene analysis.     

Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica

Soil and sediment samples from James Ross Island were analyzed for their PCB, OCP and PAH contents. Soil concentrations ranged between 0.51 and 1.82 ng g(-1) for seven indicator PCB congeners, between 0.49 and 1.34 ng g(-1) for HCH congeners, between 0.51 and 3.68 ng g(-1) for the sum of p,p'-DDT, DDE, and DDD, and between 34.9 and 171 ng g(-1) for the sum of 16 EPA PAHs. Sediment levels from 0.32 to 0.83 ng g(-1) were found for PCBs, from 0.14 to 0.76 ng g(-1) for HCHs, from 0.19 to 1.15 ng g(-1) for DDTs, and from 1.4 to 205 ng g(-1) for PAHs. A prevalence of low-mass PAHs, less chlorinated PCBs, and more volatile chemicals indicates that the long-range atmospheric transport from populated areas of Africa, South America, and Australia is the most probable contamination source for the solid matrices in James Ross Island.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

GC-profiles of chlorinated terpenes (Toxaphenes) in some Finnish environmental samples

The profiles of chlorinated terpenes in Finnish environmental samples were compared by GLC-SIM technique with those of toxaphene and Eastern European “dark”. The profiles in the seal blubber in the Northern and in the Eastern Baltic Sea proved to be similar. Chlorinated terpenes were found to be present in Finnish human milk.The spent bleach liquor of pine kraft pulp mill contained components having similar retention times and responses to those from toxaphene components.